Method of controlling the growth of weeds



United States Patent 3,399,988 METHOD OF CONTROLLING THE GROWTH OF WEEDS Stassen Y. C. Soong, Taipei, Taiwan, China, Byron H. Lake, Greenville, Miss.,-and Don R. Baker, Pinole, Califi, assignors to Stautfer Chemical Company, New York, N.Y., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 308,661, Sept. 13, 1963. This application July 15, 1966, Ser. No. 565,418

8 Claims. (CI. 71-94) ABSTRACT OF THE DISCLOSURE N-alkyl sulfonyl glycolamides useful as effective herbicides corresponding to the formula 0 R2 Rlso ocHziiN s in which R is selected from the group consisting of alkyl, alkenyl, haloalkenyl, haloalkyl, haloalkenyl thiophene, phenylalkyl, naphthyl, phenyl, and substituted phenyl wherein the substituents are selected from the group consisting of halogen, alkyl and nitro; and R and R are independently selected from the group consisting of hydrogen, alkyl, alkenyl, cyclic alkyl, cyclic alkenyl, phenyl, phenylalkyl, :furfuryl, alkoxyalkyl :and cyclic alkyl ethers. Representative compounds are O-benzenesulfonyl-N-isopropyl glycolamide, -O-methanesulfony-l- N-n-butyl glycolamide, O-p-bromobenzenesulfonyl-N- n-butyl glycolamide, O-methanesulfonyl-N,N-diallyl glycolamide, O-i-butylsulfonyl-N,N-diallyl glycolamide, O i butylsulfonyl-N,N-(Z-ethylpentamethylene) glycolamide, O-i-butylsulfonyl N -sec-butyl glycolamide.

This application is a continuation-in-part of application Ser. No. 308,661, filed Sept. 13, 1963, now abandoned.

This invention relates to certain new and novel compositions of matter and their use as herbicides. More particularly, the present invention relates to novel compounds of the structure R2 aisogoomi m wherein R is a radical selected from the class consisting of alkyl, alkenyl, haloalk-yl, haloalkenyl, phenyl, substituted phenyl wherein the substituents are selected from the group consisting of halogen, alkyl and nitro; thiophene, phenylalkyl and naphthyl, and R and R are selected from the groups consisting of hydrogen, alkyl, alkenyl, cyclic alkyl, cyclic alkenyl, phenyl, phenylalkyl, furfuryl, alkoxy-alkyl and cyclic alkyl ethers. By cyclic alkyl is meant a radical such as cyclohexyl which may be attached at the R and/or R position and, in addition, radicals such as hexamethylene which would attach at R and R to form a ring utilizing the N atom as a ring member. Cyclic alkyl ethers is meant to convey an alkyl ether in which the alkyl portions of the ether are attached to the N atom at the R and R positions so as to form a ring structure with the N atom.

The preferred compounds ofthe instant invention include compounds wherein R is an alkyl having one to twelve carbon atoms, lower alkenyl, haloalkyl having one to twelve carbon atoms, haloloweralkenyl, alkyl substituted phenyls wherein the alkyl contains up to twelve carbon atoms, phenyl lower alkyl, or loweralkoxyalkyls; R is hydrogen, alkyl having up to 8 carbon atoms, or lower alkenyl; and R is hydrogen, alkyl having up to 8 3,399,988 Patented Sept. 3, 1968 carbon atoms, or lower alkenyl. In the foregoing the term lower is meant to imply alkyls or alkenyls containing up to and including 5 carbon atoms.

These new and novel compounds of the present invention may be made by reacting the appropriately substituted glycolamide and the appropriate sulfonyl chloride in the presence of an organic base such as triethylamine.

Typical examples of the method of synthesis are as follows:

Example 1.O-benzenesulfonyl-N-isopropyl glycolamide To the benzene (100 ml.) solution of N-isopropyl glycolamide (11.7 g., 0.10 mole) and benzenesulfonyl chloride (12.7 ml., 0.10 mole) was added 15.2 ml. of triethylamine at 1520 C. over a period of five minutes with stirring. The mixture was allowed to stir for one hour at 20-32C. The mixture was washed with water (100 ml.), dilute hydrochloric acid (100 ml.) and water and then dried over magnesium sulfate and evaporated in vacuo to yield 22 g. of a light yellow liquid. On standing the liquid crystallized. This was recrystallized using n-=butyl ether, washed with n-zbutyl ether and cyclohexane to yield 13.5 g. of crystals. M.P. 64-66C.

Example 2.-O-methanesulfonyl-N-n-butyl glycolamide To the benzene (100 ml.) solution of N-n-butyl glycolamide (13.1 g., 0.10 mole) and methanesulfonyl chloride (7.7 ml., 0.10 mole) was added triethylamine (14 ml., 0.10 mole) at 16-23 C. over a period of twenty minutes with stirring and cooling. It was then stirred at 20-27 C. for one hour. The mixture was washed with water (100 ml.), dilute hydrochloric acid (100 ml.) and water (100 ml.) and dried over magnesium sulfate. Evaporation in vacuo yielded 17 g. of an oil which on scratching formed crystals. This was recrystallized from cyclo hexanezether and washed with 50:50 ether-carbon tetrachloride to yield 8 g. of a first fraction (M.P. 5456 C.) and 1 g. of a second fraction (M.P. 52-53 C.).

A'nalysisFound: Sulfur 15.5%. Calc.: Sulfur 15.4%.

Example 3.O-p-bromobenzenesulfonyl-N-n-butyl glycolimide To the benzene (100 ml.) solution of N-n-butyl glycolamide (6.5 g., 0.05 mole) and p-bromobenzenesulfonyl chloride (12.8 g., 0.05 mole) was added the triethylamine (7 ml., 0.05 mole) in one portion at 13 C. The temperature was kept at 13-20 C. with stirring and cooling until the exothermicity had ceased and then at 20-25 C. for 1 /2 hours.

The mixture was washed with water (100 ml.), dilute hydrochloric acid (100 ml.) and water. It was then dried over magnesium sulfate and evaporated in vacuo to yield a light yellow oil that soon crystallized to yield a crystalline mass. This was recrystallized from ml. of n-butyl ether to yield 13 g. of product. M.P. 76-77 C.

Analysis.Found: Bromine 22.5%, sulfur 8.98%. Calc.: Bromine 22.8%, sulfur 9.15%.

Example 4.0-methanesulfonyl-N,N-di-n-propyl glycolamide To the ether (100 ml.) solution of the N,N-di-n-propyl glycolamide (15.9 g., 0.10 mole), methane sulfonyl chlo ride (7.7 ml., 0.10 mole) was added triethylamine (14 ml., 0.10 mole) at 15-18 C. over a period of 45 minutes with stirring and cooling. The mixture was stirred for forty minutes and then washed with water (50 ml.), dilute hydrochloric acid (50 ml.) and water (50 ml.). The ether solution was dried over magnesium sulfate and evaporated in vacuo at 80 C. (20 mm.) to yield 19.5 g. of a light yellow oil. Cooling with Dry Ice induced crystals. The

crystals were washed with n-butyl ether and cyclohexane to yield 13 g. of crystals. M.P. 35-37 C.

Analysis.-Found: Sulfur 13.5%. Calc: Sulfur 13.5%. These novel compounds of the present invention have also been found to possess valuable herbicidal properties.

4 about thirty to fifty plants of each of the selected weed species in each flat. The flats are watered after planting and the following day each fiat is sprayed at a rate of 20 lbs. of the compound under test in 80 gallons of solution per acre. A No. 152 De Vilbiss atomizer is used to spray the c I e D a I Th1s herbicidal activity of the compounds of the present solution on the 8011 surface. Two weeks later the degree mventlon was demonstrated by the following test. of weed control 1s deternnned by comparing the amount Seven weed species were mdiscrimrnately selected for of germination and growth of each weed 1n the treated testing each compound from the group consisting of crabflats w1th the weeds in several untreated control flats. In grass, water grass, foxtall, w1ld oats, lambs-quarter, redreporting the results, the herblcldal effect of each comrott plgweed, Junsonweed, field bindweed, red oats, muspound w1th respect to each weed species was checked septard, annual bluegrass, dock and Indian mustard. Seeds of arately and rated from 0 to 3 (0no control, 1-part1a1 the seven slected weed species are planted 1n individual controls, 2good control, 3-complete control). The sum rows one-half inch deep in Santa Cruz sandy loam SO11 of these ratmg based on the seven weed spec1es employed contained in compressed paper flats 8% by 6 /2 WhlCh 15 18 then called the activity index (A1.) and 15 indicated are 2% deep. Enough weed seeds are planted to give 1n the following table.

H B 80 0 CHzCN Corn- R1 R2 R3 Activity pound Index 1 p-Methylphenyl I-Iydronen i-Propyl 2 Phenyl do. n-Butyl 20 do.- do.-- i-Propyl 20 Meth -.-.d0.- n-Butyl 18 p-Brornophenyl do- .d 15 Methyl..- .d0.-.- 16 PhenyL... Ethyl. 21 Methyl..- do..- 21 p-Br0mophenyl-. dodo 17 3,4-dich1or0phenyl... Hydro en l-Propyl 11 Eth d0 n-Butyl 11 Methyl AllyL. Allyl 20 3,4-dichlorophenyl. ..do .do 18 0..... Hydrogen n-Propyl 16 Methyl n-Propyl ..do 21 p-Chlorophenyl. 0 do 17 p-Bromophcnyl. n-Butyl n-Butyl 9 Methyl Hexamethylene 18 Hexamethylene 15 h Hcxarnethylene 17 Methy 2-rnethyl-pentamethylene 21 (la Pentamethylene 20 Benzyl Hexarnethyleno 20 do Pentamethylene 18 p-Nitrophenyl n-PropyL. n-Propyl 10 Naphthyl Ally] All 12 p-Nitrophenyl Hexamethylene 14 p-Fluorophenyl Hexamethylone 19 Methyl. i-Butyl l-Butyl 6 p-Methylphenyl Hexamcthylene 20 Methyl Hydrogen Cyclohexyl 17 p-Chlorophenyl d0 l-Butyl 18 p-NitrophenyL. do do 14 do do i-Propy 12 p-Ohlorophenyl do Cyclohexyl 9 p-Nitropheny1.-- d do 6 CFClzCC12 Hexamethyleno 16 h Methyl Methy 12 3-oxa-pentylrnethylene-- 10 Hydrogen Cyclohexyl 9 ..do......... 5 ..do. 12 43.- yl 5 44.. Hydrogen. 9 45.- .do ..d 8 46 Tetrarnethylene 17 47 Tetramethylene 13 48.. Tetramethylene 13 49.- Hexamethylene 15 50.. Butyl 7 51.- Cyclohex 13 52 4-dichloro 5 53 .d 5 54 4 ylene 14 55 m-Nitropheny Hexamethyleno 13 56.. p-Fluorophenyl. Pcntamethylene 9 57.- 3 4-d1chlorophenyl Hydrogen Isopropoxy ropyl 4 58.. Hexamethylene 9 59.- Hexamethylene 16 Hexamethylene 13 61 MethyL. phenyl 7 do do 20 p-Bromophenyl Hexamethylene 7 Methyl. Ethyl n-Butyl 1g Ethyl do (in 21 n-Buty do do 20 o-Nitrophenyl do do 14 p-FluorophenyL- do do 13 p-Nitrophenyl... do dn 12 p-Chlorophenyl do do 13 n-Butyl. Methyl-. Phenyl 16 p-ChlorophenyL. do do 16 do Hydrogen Isopropoxy-propyl 11 Methyl.-. do Pheny 91 Ethyl do do 6 Buty1..-.. rln 9 CHC1=CC1 Hexamethylene 9 18 :0 I-Iexamethylene 18 2 Ra Activity Index Ethyl Butyl 13 Hyd rnm n Cyclohexyl 7 fi Allyl 19 H examethylene 20 Ethyl. But 16 4-methyl-pentamethylene 21 9 4-methyl-pentamethylene 20 3-methyl-pentamethylene 20 3-methyl-pentamethylene 17 4-methyl-pentamethylene 16 4-methylpentamethylene 20 4-methyl-pentamethylene 13 3-methyl-pentamethylene 12 3-methyl-pentamethylene 17 3-methyl-pentamethylene 18 th 4-methyl'pentamethylene 18 d 3-methyl-pentamethylene 21 Methyl Methyl Butyl 30 1 Butyl 20 Phenyl.-- 19 EthyL 21 Butyl 20 Methyl- 21 Ethyl. 21 Methyl. 21 thyl. 18 ButyL. 21 .do- 21 Phenyl- 18 .do yl 15 Ethyl. 2-methyl-p entamethylene 18 Butyl. Z-methyl-pentamethylene 19 112 Methyl. Hydrogen Methyl 7 Ethyl do do 13 ButyL. do do 14 Phenyl do rln 15 Methyldo Propyl 21 Ethy do do.. 20 Methyl. do Butyl 17 Buty do do 19 Pheny do Propyl 15 "do do utyl 16 p-Toluyl do do 18 do do Propyl. 17 p-E thylpheuyl Hexamethylene 17 125 4-dodecylphenyl Hexamethylene 16 126 Phenyl 2-methyl-pentamethylene 16 127 p-Toluyl I Z-methyl-pentamethylene 18 128 Methyl- Ethyl Cyclohexyl 21 129 Buty do do 12 do 18 dn 13 A pentalene 15 A pentalene 19 A pe'ntalene 16 A pentalene 21 henyl 19 do 21 do 6 13 do 5 0 Hexamethylene 21 141 hyL. Allyl Allyl 142 d d d do... d .do. Hydrogend do .do 1 Propyl. 2-methyl-pentamethylene 1 do 3-methyl-pex 1tamethyleno 149 Ethyl. Pentamethylene 150 Butyl. Pentamethylene Propyl. Pentamethyleno 152 Phen Pentamethylene Hydrogen l-Butyl hy pentamethylene 2-ethyl-pentamethylene 2-ethyl-pentamethylene 2-ethyl-pentamethylene utyl Com- R R2 R3 Activity pound I Index 87 Methyl 3,5-dlmethyl-4-oxopentamethyleno 18 3,5-dimethyH-oxopentamethylone 18 3,5-dimethyl-4-oxopentamethylene 19 2,5-dimethyl4-oxopentamethylene 19 18 ,5-dimethyl-4-oxopentamothylene Allyl Hydrogen 21 llyl 21 cthyl-pontamethylene 21 3-methyl-pentamethylene 21 4-methyl-pentamethylene 21 Z-methyl-pentamethyleno 16 2-methyl-pontnmethylene 12 l-Propyl V 18 d Sec-bntyl 16 4-methyl-pentamethylene 14 4-methyl-pentamethylene 12 Hexamethylone 19 Allyl 16 Ally1-. 1-12 n-Propyl n-Propyl 17 Hexamethylene 18 Hydrogen Benzyl 17 2-ethyl-pentamethylene I Cyclohexyl 18 Tetrahydroturturyl 13 Pentamethylene 19 228 o 2-me-pentarnethylene 18 In addition to the pre-emergence herbicidal activity indicated by the above table, the compounds of the present invention also exhibited excellent post-emergence herbicidal activity.

We claim:

1. The method of controlling the growth of weeds comprising applying to a weed habitat a phytotoxic amount of compounds of the formula 2. The method as stated in claim 1, wherein R is methyl and R and R are allyl.

3. The method as stated in claim 1, wherein R is isobutyl and R and R are allyl. v

4. The method as stated in claim 1, wherein R is isobutyl and R and R taken together are Z-ethyl-pentamethylene.

5. The method as stated in claim 1, wherein R is isobutyl, R is hydrogen and R is sec-butyl.

6. The method as stated in claim 1, wherein R is isobutyl, R is hydrogen and R is n-propyl.

7. The method as stated in claim 1, wherein R is isobutyl, R is hydrogen and R is isopropyl.

8. The method as stated in claim 1, wherein R is isobutyl and R and R are n-propyl.

References Cited UNITED STATES PATENTS JAMES O. THOMAS, JR., Primary Examiner. 

